APP-MCA-CFA三元复配阻燃体系改性环氧树脂基玻璃纤维复合材料及性能研究  

Modification of epoxy resin-based glass fiber composites with APP-MCA-CFA ternary flame retardant system and performance study

作　　者：董大为 郝杰 欧秋仁[1] 胡楠 桂起林 张铁夫[1] 王晓辉 Dong Dawei;Hao Jie;Ou Qiuren;Hu Nan;Gui Qilin;Zhang Tiefu;Wang Xiaohui(Aerospace Institute of Advanced Material&Processing Technology,Beijing 100074)

机构地区：[1]航天特种材料及工艺技术研究所,北京100074

出　　处：《化工新型材料》2024年第6期239-246,共8页New Chemical Materials

摘　　要：首次以聚磷酸铵(APP)为酸源和主阻燃剂,以高氮含量的三聚氰胺氰尿酸盐(MCA)为气源,以大分子型三嗪成炭剂(CFA)为炭源,组成APP-MCA-CFA三元复配阻燃剂体系。将其用于环氧树脂体系的阻燃改性,通过极限氧指数(LOI)、垂直燃烧等级、锥形量热、扫描电镜(SEM)、热失重分析(TG)和动态力学分析(DMA)等实验分析了它们之间的协同效应。结果表明:与单独使用APP阻燃剂相比,三元复配阻燃剂体系(20%APP-5%MCA-5%CFA,均为质量分数)表现出显著的协同阻燃效应,LOI值提升至62.0%,热释放速率峰值(PHRR)降低至401kW/m^(2),总热释放量(THR)下降至37.3MW/m^(2)。成炭分析结果表明,APP-MCA-CFA三元复配阻燃剂体系的引入使环氧树脂在高温下形成孔洞直径约5μm的形貌均一且规整的微米级膨胀炭层。DMA实验表明MCA和CFA可以通过粒子表面的胺基参与环氧固化反应,提高环氧固化交联密度,在一定程度抵消APP阻燃剂粉体加入导致的环氧机械性能下降。APP-MCA-CFA三元复配阻燃体系可用于环氧树脂基玻璃纤维复合材料的阻燃改性,垂直燃烧等级提升至UL-94 V0级,LOI值提升至66.3%。该研究为开发综合性能优异的阻燃环氧树脂基复合体系提供了一种简单易行的途径。The ternary APP-MCA-CFA flame retardant system was composed of ammonium polyphosphate(APP)as the acid source and the main flame retardant,melamine cyanurate(MCA)with the high nitrogen content as the gas source,and triazine-based macromolecular carbon-forming agent(CFA)as the carbon source for the first time.We used this ternary APP-MCA-CFA system in the flame retardant modification of epoxy resin and then studied the synergistic flame retardancy effect of this ternary APP-MCA-CFA system via limiting oxygen index(LOI)test,vertical combustion grade,conical calorimetry tests,scanning electron microscopy(SEM)and thermogravimetric analysis(TG).The results displayed that this ternary APP-MCA-CFA system(20wt%APP-5wt%MCA-5wt%CFA)exhibited apparent synergistic flame retardancy effect compared with APP alone.The LOI increased to 62.09%,the peak of heat release rate(PHRR)decreased to 401 kW/m^(2),and the total heat release rate(THR)decreased to 37.3MW/m^(2).According to the analyses of char residues,the introduction of ternary APP-MCA-CFA system resulted in the formation of a uniform and regular micron-scale expanded char layer with pore diameters of approximately 5μm at high temperatures.DMA experiments showed that MCA and CFA could participate in epoxy curing reaction through the amine groups on the particle surface,which improved the cross-linking density of epoxy curing and offset the reduction of mechanical properties caused by the addition of APP flame retardant powder.Moreover,we incorporated this ternary APP-MCA-CFA system for flame retardant modification of epoxy resin-based glass fiber reinforced composite(GFRC),achieving a vertical burning grade of UL-94 V0 and a LOI value of 66.3%.This study provided an effective strategy to develop epoxy resin-based composite systems with excellent comprehensive performance.

关 键 词：环氧树脂 三元复配阻燃体系 协同阻燃效应 玻璃纤维增强复合材料 

分 类 号：TB332[一般工业技术—材料科学与工程] TQ323.5[化学工程—合成树脂塑料工业]